EP0211084A1 - Zelle mit festem elektrolyten - Google Patents

Zelle mit festem elektrolyten Download PDF

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Publication number
EP0211084A1
EP0211084A1 EP86900839A EP86900839A EP0211084A1 EP 0211084 A1 EP0211084 A1 EP 0211084A1 EP 86900839 A EP86900839 A EP 86900839A EP 86900839 A EP86900839 A EP 86900839A EP 0211084 A1 EP0211084 A1 EP 0211084A1
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EP
European Patent Office
Prior art keywords
solid electrolyte
solid
heteropolyacid
cell
represented
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP86900839A
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English (en)
French (fr)
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EP0211084A4 (de
EP0211084B1 (de
Inventor
Tetsuichi Kudo
Go Kawamura
Akira Ishikawa
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hitachi Ltd
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Hitachi Ltd
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Publication date
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Publication of EP0211084A1 publication Critical patent/EP0211084A1/de
Publication of EP0211084A4 publication Critical patent/EP0211084A4/de
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Publication of EP0211084B1 publication Critical patent/EP0211084B1/de
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/403—Cells and electrode assemblies
    • G01N27/406—Cells and probes with solid electrolytes
    • G01N27/407—Cells and probes with solid electrolytes for investigating or analysing gases
    • G01N27/4073—Composition or fabrication of the solid electrolyte
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G39/00—Compounds of molybdenum
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G39/00—Compounds of molybdenum
    • C01G39/006—Compounds containing, besides molybdenum, two or more other elements, with the exception of oxygen or hydrogen
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G41/00—Compounds of tungsten
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G41/00—Compounds of tungsten
    • C01G41/006—Compounds containing, besides tungsten, two or more other elements, with the exception of oxygen or hydrogen
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect
    • G02F1/1514—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material
    • G02F1/1523—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material comprising inorganic material
    • G02F1/1525—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material comprising inorganic material characterised by a particular ion transporting layer, e.g. electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/08—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances oxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1007—Fuel cells with solid electrolytes with both reactants being gaseous or vaporised
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04082—Arrangements for control of reactant parameters, e.g. pressure or concentration
    • H01M8/04089—Arrangements for control of reactant parameters, e.g. pressure or concentration of gaseous reactants
    • H01M8/04119—Arrangements for control of reactant parameters, e.g. pressure or concentration of gaseous reactants with simultaneous supply or evacuation of electrolyte; Humidifying or dehumidifying
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a hydrogen ion (generally its hydrate)-conductive solid electrolyte. Particularly, it relates to a solid electrolyte which is suitably used in electrochemical equipment such as hydrogen-oxygen fuel cell, hydrogen sensor or pH sensor.
  • An object of the present invention is to provide a novel solid electrolyte which is suitably used in fuel cells, various sensors, electrochromic display elements or the like.
  • the heteropolyacid containing carbon as a heteroatom to be used in the present invention exhibits a remarkable proton conductivity, that is, it is a proton-conductive solid electrolyte.
  • the heteropolyacid has advantages in that its preparation is simple and that it can be molded more easily than other heteropolyacids. Further, the- heteropolyacid is still advantageous in that a firm thin film can be produced from an aqueous solution thereof.
  • a heteropolyacid solid electrolyte is a solid comprising a heteropolyanion represented by the general formula, M' x M y O z m - , and a hydrated proton represented by the general formula, H(m' H 2 0) + , wherein proton is conducted.
  • M is generally tungsten(W) or molybdenum(Mo) and P,Si,As and the like are known as the heteroatom M'.
  • the solid electrolyte according to the present invention is represented by the above formula wherein M' is carbon (C) and is a novel electrolyte which has not been known up to this time.
  • heteropolyacids of the prior art have been prepared by liquid phase reaction between polytungstic acid (or polymolybdic acid) and an acid 'containing a heteroatom (for example, dodeca acid)
  • the solid electrolyte of the present invention is prepared by the reaction between tungsten carbide and a solution of hydrogen peroxide.
  • the heteropolyacid of the present invention is a solid heteropolyacid containing carbon as a heteroatom which comprises a heteropolyanion represented by the general formula, M' x M y O z m - (wherein the ratio of x to y is between 1: 12 and 4:12) and a hydrated proton represented by the formula, H(m' H 2 O) + .
  • M' is C and M is at least one element selected from the group consisting of W and Mo.
  • the above formula can be also represented by the formula : WO 3 ⁇ aCO 2 ⁇ bH 2 O 2 cH 2 O (wherein 0.083 ⁇ 2 ⁇ 0.25, 0.05 ⁇ b ⁇ 1 and 0.16 ⁇ c ⁇ 4).
  • H 2 0 2 hydrogen peroxide
  • WC tungsten carbide
  • the obtained solid electrolyte stock solution was placed in a flat-bottomed glass vessel, heated until just before its solidification and allowed to stand at a room temperature. By allowing to stand for 24 hours or over, a glassy plate was obtained.
  • This solid did not exhibit any X-ray diffraction pattern, that is, it was amorphous. Further, the solid had a molar ratio of C to W of about 1 : 12. When the solid was heated, it first lost moisture and was decomposed with release of C0 2 at about 300°C into W0 3 . Infrared or Raman spectroscopic analysis of the solid showed the presence of a strong band of about 950 to 1000 cm- l .
  • the infrared spectroscopic analysis thereof showed the presence of an absorption of about 1300 to 1400 which was inherent in the substance.
  • 13 C - NMR spectroscopic analysis of the above solid electrolyte stock solution showed the presence of a resonance absorption at about 167 ppm. It is apparent from the above results that the obtained solid is a kind of heteropolyacids containing carbon as a heteroatom.
  • a cell shown in Fig. 1 was produced by the use of the above solid plate.
  • numeral 1 refers to the above solid plate.
  • Platinum springs 4 and 5 press platinum electrodes 2 and 3 against the both surfaces of the solid plate 1, respectively.
  • the other ends of the springs 4 and 5 are taken out as electric leads 6 and 7.
  • Glass tubes 8 and 9 are bonded to the solid electrolyte 1 with an epoxy adhesive 10.
  • Steam-saturated hydrogen was fed at 10°C via inlets 11 and 12 and discharged via outlets 13 and 14, respectively.
  • the electromotive force generated between the electric leads 6 and 7 in this step was 0 V.
  • the resistance of the solid electrolyte was estimated based on the response of the voltage given when a pulse of an electric current was applied on the cell shown in Fig. 1.
  • the resistance was about 500Q at 20°C. Since the solid electrolyte had a thickness of 0.2 cm and the electrode area was 0.2 cm 2 , the specific resistance was 500Q cm.
  • a solid electrolyte stock solution was prepared in a similar manner as the one described in Example 1.
  • the stock solution was placed in a flat-bottomed glass vessel. Air of a room temperature (about 20°C) was blown into the vessel to thereby evaporate the moisture, thus solidifying the solution.
  • the obtained solid plate was amorphous and had a molar ratio of C to W of 1 : 9.
  • the solid plate was heated, it began to release C0 2 at a temperature of about 200°C and decomposed into W0 3 .
  • the other characteristics thereof were similar to those of the solid obtained in Example 1. Accordingly, it was apparent that the solid obtained in Example 2 was a heteropolyacid (solid) containing carbon as a heteroatom.
  • Example 1 A similar cell as the one produced in Example 1 was produced by the use of the above solid plate.
  • the relationship between the electromotive force generated between the leads 6 and 7 and the hydrogen concentration was examined in a similar manner as the one described in Example 1.
  • the concentration dependence represented by the equation 1 was confirmed and the solid was found to be a hydrogen ion-conductive solid electrolyte.
  • the specific resistance of the solid electrolyte was 250Q cm.
  • Example 2 The same procedure as the one described in Example 1 was repeated except that a mixture comprising WC and MO 2 C at a molar ratio of 18 : 1 instead of WC was reacted with H 2 0 2 to obtain a solid electrolyte stock solution.
  • the stock solution was placed in a flat-bottomed glass vessel and solidified by blowing air.
  • the obtained solid was a heteropolyacid having a molar ratio of C to metal (W + Mo) of about 1 : 9.
  • a similar cell as the one shown in Fig. 1 was produced by the use of the above plate.
  • the relationship between the electromotive force generated between the leads 6 and 7 and the hydrogen concentration was examined to observe the concentration dependence represented by the equation 1, thus confirming that the obtained heteropolyacid containing carbon, tungsten and molybdenum was also a hydrogen ion-conductive solid electrolyte.
  • the solid electrolyte had a specific resistance of about 300Q (at 20°C).
  • the solid electrolyte of the present invention has excellent effects.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Physics & Mathematics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Sustainable Energy (AREA)
  • Sustainable Development (AREA)
  • Nonlinear Science (AREA)
  • Analytical Chemistry (AREA)
  • Pathology (AREA)
  • Immunology (AREA)
  • General Health & Medical Sciences (AREA)
  • Biochemistry (AREA)
  • Optics & Photonics (AREA)
  • Molecular Biology (AREA)
  • Conductive Materials (AREA)
  • Measuring Oxygen Concentration In Cells (AREA)
  • Fuel Cell (AREA)
  • Catalysts (AREA)
EP86900839A 1985-01-25 1986-01-16 Zelle mit festem elektrolyten Expired - Lifetime EP0211084B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP60010840A JPS61171069A (ja) 1985-01-25 1985-01-25 固体電解質
JP10840/85 1985-01-25

Publications (3)

Publication Number Publication Date
EP0211084A1 true EP0211084A1 (de) 1987-02-25
EP0211084A4 EP0211084A4 (de) 1989-09-26
EP0211084B1 EP0211084B1 (de) 1992-07-01

Family

ID=11761547

Family Applications (1)

Application Number Title Priority Date Filing Date
EP86900839A Expired - Lifetime EP0211084B1 (de) 1985-01-25 1986-01-16 Zelle mit festem elektrolyten

Country Status (5)

Country Link
US (1) US4699851A (de)
EP (1) EP0211084B1 (de)
JP (1) JPS61171069A (de)
DE (1) DE3685860T2 (de)
WO (1) WO1986004320A1 (de)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106596684A (zh) * 2016-12-01 2017-04-26 深圳市深安旭传感技术有限公司 一种氢气传感器

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4691786B2 (ja) * 2001-01-15 2011-06-01 トヨタ自動車株式会社 燃料電池電解質膜の高温挙動解析治具および方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3617945A1 (de) * 1985-05-29 1986-12-04 Hitachi, Ltd., Tokio/Tokyo Polywolframsaeure mit peroxogruppen, verfahren zu ihrer herstellung und ihre verwendung
US4634585A (en) * 1984-05-25 1987-01-06 Hitachi, Ltd. Heteropoly acid containing carbon as hetero atom

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS50536A (de) * 1973-05-11 1975-01-07
JPH05189135A (ja) * 1992-01-14 1993-07-30 Canon Inc 座標入力装置

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4634585A (en) * 1984-05-25 1987-01-06 Hitachi, Ltd. Heteropoly acid containing carbon as hetero atom
DE3617945A1 (de) * 1985-05-29 1986-12-04 Hitachi, Ltd., Tokio/Tokyo Polywolframsaeure mit peroxogruppen, verfahren zu ihrer herstellung und ihre verwendung

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
NATURE, vol. 312, 6th December 1984, pages 537-538; T. KUDO: "A new heteropolyacid with carbon as a heteroatom in a Keggin-like structure" *
See also references of WO8604320A1 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106596684A (zh) * 2016-12-01 2017-04-26 深圳市深安旭传感技术有限公司 一种氢气传感器

Also Published As

Publication number Publication date
JPS61171069A (ja) 1986-08-01
EP0211084A4 (de) 1989-09-26
EP0211084B1 (de) 1992-07-01
US4699851A (en) 1987-10-13
DE3685860D1 (de) 1992-08-06
DE3685860T2 (de) 1993-02-25
WO1986004320A1 (fr) 1986-07-31

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